CN103833035A - Preparation method of silicon carbide - Google Patents
Preparation method of silicon carbide Download PDFInfo
- Publication number
- CN103833035A CN103833035A CN201410081038.6A CN201410081038A CN103833035A CN 103833035 A CN103833035 A CN 103833035A CN 201410081038 A CN201410081038 A CN 201410081038A CN 103833035 A CN103833035 A CN 103833035A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- preparation
- gas
- silicon
- heater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
- C01B32/97—Preparation from SiO or SiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
- C01B32/984—Preparation from elemental silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0869—Feeding or evacuating the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0883—Gas-gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0884—Gas-liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0886—Gas-solid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0888—Liquid-liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
- B01J2219/0898—Hot plasma
Abstract
The invention provides a preparation method of silicon carbide, belongs to the technical field of semiconductor preparation, and is used for solving the problems of serious environmental pollution and low price caused by mass production of silicon carbide with relatively low purity by the existing simple outdoor silicon carbide preparation equipment. The preparation method of silicon carbide comprises the following steps: in a furnace body in a vacuum environment or under the protection of inert gas, dissolving or evaporating a silicon raw material for producing silicon carbide in a high-temperature environment over 1300 DEG C and enabling the dissolved or evaporated silicon raw material to react with carbon-containing gas or liquid to generate silicon carbide. According to the method provided by the invention, the carbon-containing gas without metal impurities replaces the carbon raw materials such as petroleum coke, resin, asphalt, ink, carbon fiber, coal and charcoal in the existing preparation method; in the carbonization reaction, the silicon raw material is in a molten or evaporated gasified state and reacts in air; without needing a carrier, the mixing of impurities is reduced, and the prepared silicon carbide has relatively high purity.
Description
Technical field
The invention belongs to semi-conductor preparing technical field, relate to a kind of as the raw-material high-purity carborundum preparation method of semiconductor device substrates.
Background technology
Existing silicon carbide preparation method is mixed in proportion silica raw material and carbon raw, prepares by the method for acheson furnace heating; Carbon raw refers to the refinery coke that contains carbon, resin, pitch, China ink, carbon fiber, coal, charcoal etc.Carbon reaction in silicon-dioxide and carbon source in silica forms silicon carbide, but in these silicas and carbon source, contain more metallic impurity ash content, also there is chemical reaction in these impurity under heat environment, the purity of silicon carbide itself is also had to considerable influence, make the purity of silicon carbide not high, can not meet the market requirement of high purity silicon carbide, and the waste gas that reaction produces causing larger pollution to environment, there are a lot of urgent problems in existing preparation method.
In addition, silicon carbide is originally produced by simple equipment, and this simple outdoor lower silicon carbide of a large amount of production purity of equipment, can cause very large pollution to environment, cheap, does not meet environmental requirement, can not meet the demand in market.
Summary of the invention
The present invention is directed to prior art and have the problems referred to above, proposed a kind of preparation method of silicon carbide, first technical problem to be solved by this invention is to provide another and does not adopt the carbon raws such as refinery coke, resin, pitch, China ink, carbon fiber, coal, charcoal to prepare the preparation method of high-purity carborundum; Second technical problem to be solved by this invention is to provide this preparation method's preparation facilities.
The present invention realizes by following technical proposal: a kind of preparation method of silicon carbide; it is characterized in that; in body of heater under vacuum environment or protection of inert gas, the silicon material of producing silicon carbide is melted or evaporated in the hot environment that exceedes 1300 DEG C and will melt or the silicon material of evaporation and gas or the liquid reactions Formed SiClx that contains carbon.
It is as follows that the gas that the gas that melting contains carbon contains carbon melts principle of work of the present invention: the present invention adopts the gas that contains carbon to react with silicon material, because the gas that contains carbon can be accomplished very high purity, avoid employing refinery coke, resin, pitch, China ink, carbon fiber, coal, the impurity effect of the carbon raws such as charcoal, and silicon material also can be made very high purity, ensureing on the basis of the two purity, silicon material melts or further evaporation gasification exceeding in 1300 DEG C of hot environments, while in hot environment, contains the gas of carbon or liquid decomposes or cracking goes out carbon with melting or the silicon material that further evaporation is gasified reacts, generate highly purified silicon carbide.
In the preparation method of above-mentioned silicon carbide, described silicon material is silicon.Silicon is highly purified Pure Silicon Metal, or is semiconductor silicon, claims again silicon metal.
In the preparation method of above-mentioned silicon carbide, described silicon material is purity higher than 99.99% silicon.Silicon material purity just can be used 99.99% time, and the semiconductor silicon of this purity is material common on market, does not need further to purify, and the market that is embodied as of the present invention can be accepted.If expect the silicon carbide that purity is higher, also can use purity up to 99.9999999999% semi-conductor rank silicon.
In the preparation method of above-mentioned silicon carbide, aerial in body of heater of the position of silicon material and the gas reaction Formed SiClx that contains carbon.Silicon material and the gas that contains carbon are aloft reacted, just can avoid the pollution of the carriers such as crucible to reaction, further reduced the possibility that impurity is sneaked into, improved the purity of Formed SiClx.
In the preparation method of above-mentioned silicon carbide, silicon material is joined in body of heater its melting or evaporation are gasified, and be ejected in the gas that contains carbon, reaction Formed SiClx.Adopt and can make in this way silicon material have sufficient energy to react fully, improve the utilization ratio of silicon material.And adopt spray regime can increase contact area and the distance of silicon material and the gas that contains carbon and improve both mixture homogeneities.
In the preparation method of above-mentioned silicon carbide, by the gas that contains carbon or spouting of liquid to melt or the silicon material of evaporation gasification in, reaction Formed SiClx.Adopting in this way except the gas that contains carbon, can also be to adopt the highly purified liquid that contains carbon, as alcohol, ether etc.Silicon material can be put into before igniting heating, and its post-heating melts silicon material or evaporation.
In the preparation method of above-mentioned silicon carbide, joining the gas reaction Formed SiClx that makes silicon material and contain carbon in above-mentioned body of heater after silicon material and the gas that contains carbon or liquid mixing.Silicon material can do powdered, is mixed or joins together with after liquid mixing in body of heater by gas after being blown with gas, and this mode can be accurately to control proportioning, reduces the generation of waste gas.
In the preparation method of above-mentioned silicon carbide, described silicon material is siliceous compound.Except direct use silicon, can also use the siliceous compound such as quartz sand, silica.
In the preparation method of above-mentioned silicon carbide, the heat source generator that melts or evaporate the hot environment of the described silicon material of gasification is plasma generator, combustible gas combustion furnace, laser apparatus or graphite electric heater.These four kinds of heating installations can provide 2500 degrees Celsius of above temperature, meet the demand of melting or the evaporation gasification of silicon material.At normal temperatures and pressures, 1410 DEG C of the fusing points of silicon, 2355 DEG C of boiling points, but under vacuum environment, the fusing point of silicon and boiling point can reduce.And the temperature that plasma high temperature heat source produces can arrive 10000 degree, be far longer than the boiling point of silicon.
In the preparation method of above-mentioned silicon carbide, the inside of the position of silicon material and the gas reaction Formed SiClx that contains carbon in plasma generator, combustible gas combustion furnace or graphite electric heater.
In the preparation method of above-mentioned silicon carbide, the described gas that contains carbon is hydrocarbon, hydrocarbon polymer, fluorocarbon, carbon chlorine compound or contains one or several mixing in the gaseous compound of hydrocarbon fluorine element.
In the preparation method of above-mentioned silicon carbide, centered by the thermal source providing by described heat source generator, in concentrically ringed mode, the above-mentioned gas that contains carbon is provided in the preparation facilities of silicon carbide.
In the preparation method of above-mentioned silicon carbide, described in contain carbon gas to be provided in the preparation facilities of silicon carbide be the identical or different several gases of composition.Its concrete mode can, for the gas of heterogeneity is provided within the scope of same concentric(al) circles, can be also that same concentric(al) circles only provides a kind of composition gas, and different concentric(al) circless provide the gas of heterogeneity.Latter event can provide heterogeneity gas to farthest realize the carburizing reagent of silicon material according to the distribution trend of the outside radiation falloff of temperature of thermal source, high efficiency Formed SiClx.
In the preparation method of above-mentioned silicon carbide, the flow velocity of described gas is according to different from the distance of thermal source central point and adjust.The gas flow rate that the distance of distance center point is far away is slower, and the flow velocity of the nearlyer gas of distance center point distance is faster.
In the preparation method of above-mentioned silicon carbide, the silicon carbide that to be mixed with containing weight percent in described silicon material be 0.1～10%.In silicon material, add silicon carbide can play the effect that prevents that newly-generated silicon carbide from boning mutually.
A kind of preparation facilities of silicon carbide, comprise body of heater and the crucible that is positioned at body of heater, bottom at body of heater is provided with elevating bracket, above-mentioned crucible is placed on elevating bracket, it is characterized in that, described body of heater top is provided with jet orifice and faces the heat source generator of crucible, the inside of described heat source generator has the inner chamber that is communicated with heat source generator outlet, in inner chamber, be provided with airway, if go out the individual concentric(al) circles outlet of interruption-forming thereby some toroidal membranes taking airway as axis are set on heat source generator at heat source generator, on heat source generator, be also provided with the import being connected with each outlet, bottom at body of heater is provided with venting port.
The principle of work of the preparation facilities of silicon carbide is as follows: heat source generator is plasma generator or laser generator.After the airway of plasma generator or laser generator passes into argon gas, its outlet has produced plasma flame or laser, plasma generator or laser generator have formed several concentric(al) circles outlets by dividing plate, due to taking airway as axis, this plasma flame or the laser center in each concentric(al) circles outlet, the gas that contains carbon can add and keep output in advance from import, the particle of silicon material can add or add from airway from import, in the time falling into plasma flame or laser, fusing or further evaporation gasification produce carburizing reagent with the carbonaceous gas on concentric(al) circles, and the high-purity carborundum generating falls into crucible.
In the preparation facilities of above-mentioned silicon carbide, with the import of described intracavity inter-connection be silicon material import.
In the preparation facilities of above-mentioned silicon carbide, described dividing plate is two, is set in successively the outside of internal chamber wall, forms respectively the gas feed and the secondary inlet that contain carbon.The gas that secondary inlet can be used for containing carbon or and the import of shielding gas.
In the preparation facilities of above-mentioned silicon carbide, on described crucible outer side wall, be also provided with the silicon carbide generating is sucked to the suction opening in crucible.Described suction opening is connected with extraneous vacuum pump by conduit.
In the preparation facilities of above-mentioned silicon carbide, described body of heater top is provided with shielding gas import.
Compared with prior art, the preparation method of this silicon carbide adopts the not carbonaceous gas of metal impurities to replace the refinery coke in existing preparation method, resin, pitch, China ink, carbon fiber, coal, the carbon raws such as charcoal, because the purity of gas can arrive more than 99.99999%, 7 more than 9, the purity of the silicon materials such as silicon can reach 12 more than 9, in the time carrying out carburizing reagent, silicon material is the state of fusing or evaporation gasification and aloft reacts, do not need carrier, reduce sneaking into of impurity, the silicon carbide purity of preparation is higher, reach 99.9999%, this preparation method does not produce metal ash content, avoid the pollution to environment, there are larger market outlook.
Brief description of the drawings
Fig. 1 is the structural representation of the preparation facilities of silicon carbide.
Fig. 2 is the cross-sectional schematic of A-A in Fig. 1.
Fig. 3 is plasma flame temperature and the flow velocity collection of illustrative plates of the parameter of setting in embodiment 1.
In figure, 1, plasma generator; 11, airway import and electrode tip; 12, the gas feed that contains carbon; 13, secondary inlet; 14, dividing plate; 15, concentric(al) circles outlet; 151, silicon material outlet; 152, the pneumatic outlet that contains carbon; 153, pilot outlet; 16, silicon material import; 17, plasma flame; 18, inner chamber; 19, airway; 20, water coolant intake-outlet and electrode tip; 2, shielding gas import; 3, Reaktionsofen; 31, body of heater; 311, upper of furnace body; 312, body of heater middle part; 313, lower portion of furnace body; 32, sliding surface bearing; 33, driving stem; 4, crucible; 41, suction opening; 5, elevating bracket; 6, venting port.
Embodiment
Be below specific embodiments of the invention, and by reference to the accompanying drawings technical scheme of the present invention be further described, but the present invention is not limited to these embodiment.
Embodiment 1:
The preparation method of this silicon carbide adopts the preparation facilities in Fig. 1 to realize; Fig. 1 is the Reaktionsofen of preparing silicon carbide; in body of heater under the protection of rare gas element argon gas; the silicon material of producing silicon carbide is melted or evaporated in the hot environment that exceedes 1300 DEG C and will melt or the silicon material of evaporation and gas or the liquid reactions Formed SiClx that contains carbon, its concrete steps are as follows:
A, connect and the parameter of preparation facilities is set: will produce the airway import 11 of isoionic argon gas source access plasma generator 1, airway import 11 is also the electrode interface of plasma generator simultaneously, the flow of setting argon gas is 10～30L/ minute, the present embodiment is set as 20L/ minute, and plasma generator 1 switches on power and sets isoionic electric current is that 200A, arc ignition voltage are 20000V.The gas source that contains carbon is linked in the gas feed 12 and secondary inlet 13 that contains carbon; the flow of the gas that contains carbon is adjusted in 0.3～30L/ minute according to process; the gas flow that contains carbon in secondary inlet 13 is to adjust in 0.5～50L/ minute; this gas, except providing carbon, can also use as shielding gas.Shielding gas argon gas source is linked into shielding gas import 2, and to keep the argon flow amount of Reaktionsofen 3 be 10～30L/ minute, and the present embodiment is set as 20L/ minute.Pneumatic outlet 152 and pilot outlet 153 that the concentric(al) circles outlet 15 of the plasma generator 1 forming by dividing plate 14 exports 151, contains carbon for silicon material, for ensureing that silicon material and the gas that contains carbon have sufficient reaction, the diameter that silicon material goes out is 10～20mm, the present embodiment is 15mm, diameter 45～the 55mm of the pneumatic outlet 152 that contains carbon, the present embodiment is 50mm, the diameter of pilot outlet 153 is 5～15mm, the present embodiment is 10mm, and the diameter of the elevating bracket of crucible below is 200mm.
B, silicon material drop into: complete after A step, the highly purified Pure Silicon Metal taking diameter below 1mm is silicon material, silicon material be purity higher than 99.99%, silicon material is added from silicon material import 16 with the speed of 10 gram/minute.Silicon material is silicon, except silicon can also replace with siliceous compound, as silica, quartz sand etc.The input amount of silicon material refers to the amount that plasma flame 17 that plasma generator 1 produces can fully dissolve silicon material or evaporate, irrelevant with raw-material size.The flow of the gas that contains carbon refer to mix with silicon material drop into after, the carbon containing in the composition of the gas that contains carbon can be enough by the flow of silicon material carbonization.The shield gas flow rate of secondary inlet 13 refers in order to make fully high efficiency reaction of starting material, the gas that the expansion of the gas stream that contains carbon is suppressed.
In the hot environment producing at plasma flame 17, as shown in Figure 3, the nearlyer temperature of distance outlet is higher, has 12000 degree, and outwards weakens gradually for the temperature that plasma flame 17 produces.And the jet velocity of flame can find out that the speed of flame kernel is 400m/s, and it is slower more to arrive outside flame velocity, therefore, in the time that silicon material drops in plasma flame 17, to go to whereabouts from 12000 degree, in dropping process, silicon material melted or further evaporate and spray with flame, the silicon material melting or evaporate is provided in the gas that contains carbon, the gas that contains carbon passes in advance, in the present embodiment can from the pneumatic outlet 152 and the pilot outlet 153 that contain carbon, therefore, reaction is carrying out in the air in body of heater, reduce the possibility that impurity is sneaked into, reaction Formed SiClx can fall into the crucible of below, can also be by the set positions of reaction in the inside of plasma generator,, in the cavity of one section of flame export top, be arranged within and further reduce sneaking into of impurity, and there are some thermal perturbation effects after falling into body of heater.Silicon material is ejected in the gas that contains carbon and can ensures that silicon material has sufficient carbon to react, and adopt spray regime can increase contacting apart from of silicon material and the gas that contains carbon and improve both mixture homogeneities.Except the plasma generator 1 using in this example, can also replace with combustible gas combustion furnace, graphite electric heater or laser apparatus.
The gas that contains carbon is hydrocarbon, hydrocarbon polymer, fluorocarbon, carbon chlorine compound or contains one or several mixing in the gaseous compound of hydrocarbon fluorine element.Specifically, hydrocarbon can be CO, CO2, hydrocarbon polymer can be the gases such as CH4, C2H2, C3H6, fluorocarbon can be the gases such as CF4, C2F2, C3F6, carbon chlorine compound can be the gases such as CCl4, C2Cl2, C3Cl6, can also be the gaseous compound containing hydrocarbon fluorine element, as CH2F2 etc.These gases are mixed also and are fine in proportion, can be enough by silicon material carbonization as long as meet the carbon containing in the composition of the gas that contains carbon.Except gas, can also adopt the liquid that contains carbon, as alcohol, ether etc., the amount adding is that the carbon containing in composition can be enough by silicon material carbonization.
In the time passing into the gas that contains carbon, centered by the thermal source providing by heat source generator, this routine thermal source is plasma flame 17, and the preparation facilities that the gas that contains carbon is provided to silicon carbide in concentrically ringed mode is in Reaktionsofen 3.It is the different several gases of composition that the gas that contains carbon is provided in the preparation facilities of silicon carbide.It is specially the gas that heterogeneity is provided within the scope of same concentric(al) circles.The flow velocity of gas is according to different from the distance of thermal source central point and adjust.Also can be a kind of gas that composition is identical.
In order to play the effect that prevents that newly-generated silicon carbide from boning mutually, the silicon carbide that to be mixed with containing weight percent in silicon material be 0.1～10%.In addition, no matter the size of silicon material, though the degree of Nano grade, by with respect to 10 times of silicon materials silicon carbide more than size sneak into and can make resultant of reaction spray smoothly, not adhesion mutually, is mixed with 1～5% silicon carbide by weight percentage for best.
In addition, the size of silicon material is within the scope of the above, if gas flow is at the above below scope time arbitrarily above, gas does not have the effect of abundant reaction; If when the flow of above arbitrary gas exceedes the above scope, will produce unnecessary and waste.
In order further to improve purity, prevent secondary pollution, the inner side of body of heater 31 is carried out to polishing or is increased coating, coating is high molecular weight ptfe coating, and by the flow set of shielding gas at the more than 2 times of the gas flow that contains carbon.
Principle of work of the present invention is as follows: silicon material drops in plasma flame 17 and in plasma flame 17 and melts or further evaporation gasification, and along with plasma flame 17 is ejected in the gas that contains carbon, the decomposing gas that contains carbon in plasma flame 17 goes out carbon, thereby the silicon material of this carbon and melting or evaporation gasification produces carburizing reagent Formed SiClx, and the silicon carbide of generation is collected and just can obtain highly purified silicon carbide.Because the gas that contains carbon has very high purity, do not contain metallic impurity, therefore can obtain highly purified silicon carbide, and not have metallic impurity therefore can not cause the atmospheric pollution of metal ash content.
As shown in following table one, the component content analytical table that this table is semiconductor grade silicon, taking high purity silicon as starting material, by above-mentioned processing condition, test, obtain silicon carbide, remove Ta on the impact of purity after, after analysis, obtain purity and be 99.9995% silicon carbide.
Use C2H2 gas as the gas that contains carbon, by the above processing condition of recording, test, the silicon carbide that to have obtained purity be 99.9999%.Above test-results can prove, the present invention is for producing highly purified silicon carbide, is very effective production method.
The preparation facilities that the preparation method of this silicon carbide uses as shown in Figure 1, the crucible 4 that it comprises body of heater 31 and is positioned at body of heater 31, be provided with elevating bracket 5 in the bottom of body of heater 31, crucible 4 is placed on elevating bracket 5, body of heater 31 tops are provided with jet orifice and face the plasma generator 1 of crucible 4, and the plasma flame 17 producing by plasma generator 1 is prepared silicon carbide.Specific as follows:
Body of heater 31 is divided into three parts, upper of furnace body 311, body of heater middle part 312 and body of heater middle part 313, upper of furnace body 311 is connected by flange with the upper end at body of heater middle part 312, the lower end at body of heater middle part 312 is connected with body of heater middle part 313 by flange, thereby form the space of a sealing, on body of heater middle part 313, be provided with sliding surface bearing 32, driving stem 33 is housed on sliding surface bearing 32, driving stem 33 one end extend in body of heater 31 and elevating bracket 5 are set in end, crucible 4 is placed on elevating bracket 5, by so adjusting according to the temperature of the scope of silicon carbide ejection and plasma flame 17 position of crucible 4.Crucible 4 is the structure that young tripe is large, on its sidewall, be also provided with the silicon carbide generating sucked to the suction opening 41 in crucible 4, suction opening 41 be arranged on Lower Half and oblique under.Described suction opening 41 is connected with extraneous vacuum pump by conduit.Be provided with venting port 6 in the bottom of body of heater 31.
Plasma generator 1 is arranged on upper of furnace body 311, the inside of plasma generator 1 has the inner chamber 18 that connection plasma generator 1 exports, in inner chamber 18, be provided with airway 19, airway 19 is in positive Chinese word, if go out the individual concentric(al) circles outlet 15 of interruption-forming thereby some toroidal membranes 14 taking airway 19 as axis are set on plasma generator 1 at plasma generator 1, as shown in Figure 2, on plasma generator 1, be also provided with the import being connected with each outlet, the import being connected with inner chamber 18 is silicon material import 16, dividing plate 14 is two, be set in successively the outside of inner chamber 18 walls, form respectively the gas feed 12 and the secondary inlet 13 that contain carbon.Pneumatic outlet 152 and pilot outlet 153 that the concentric(al) circles outlet 15 of the plasma generator 1 forming by dividing plate 14 exports 151, contains carbon for silicon material.Also be provided with water coolant intake-outlet 20 at plasma generator 1 sidepiece, water coolant intake-outlet 20 is also the electrode interface of plasma generator.
Upper of furnace body 311 has top, is provided with shielding gas import 2 at top, and shielding gas import 2, near the inner side-wall of body of heater 31, is also provided with the viewing window for observing body of heater 31 inner cases at top.
The principle of work of the preparation facilities of silicon carbide is as follows: after the airway 19 of plasma generator 1 passes into argon gas, its outlet has produced plasma flame 17, plasma generator 1 has formed several concentric(al) circles outlets 15 by dividing plate 14, due to taking airway 19 as axis, this plasma flame 17 is in each concentric(al) circles outlet 15 center, the gas that contains carbon can add and keep output in advance from import, the particle of silicon material can add or add from airway 19 from import, in the time falling into plasma flame 17, fusing or further evaporation gasification produce carburizing reagent with the carbonaceous gas on concentric(al) circles, and the high-purity carborundum generating falls into crucible 4.
Embodiment 2:
The content of embodiment 2 is basic identical with embodiment 1, difference is, before heating igniting, silicon ingot is put into body of heater, silicon ingot while igniting afterwards in body of heater melts or evaporation gasification, under hot environment, the gas that contains carbon or liquid carrying being fed in the silicon material of melting or evaporation gasification again, react Formed SiClx.Principle of work is: silicon material melts or further evaporation gasification in hot environment, contains the decomposing gas of carbon or cracking simultaneously and go out carbon and be ejected into melt or further in boil-off gas SiClx starting material in hot environment.
The content of embodiment 3 is basic identical with embodiment 1; difference is; silicon material does powdered; after being blown by gas, be mixed with gas or join together with after liquid mixing in body of heater; in the hot environment that exceedes 1300 degrees Celsius, silicon material and the gas that contains carbon or the reaction raw materials of liquid mixing are joined in body of heater, this is that reaction can or be filled with the gas reaction Formed SiClx that makes silicon material and contain carbon in the environment of argon shield gas in vacuum environment.This mode can be accurately to control proportioning, reduces the generation of waste gas.
Embodiment 4
Embodiment 4 is basic identical with embodiment 1 or embodiment 2, and difference is, embodiment adopts vacuum environment to enter reaction.At normal temperatures and pressures, 1410 DEG C of the fusing points of silicon, 2355 DEG C of boiling points, but under vacuum environment, the fusing point of silicon and boiling point can reduce.And the temperature that plasma high temperature heat source produces can arrive 10000 degree, be far longer than the boiling point of silicon.
Embodiment 5
Embodiment 5 and embodiment 1,2,3 or 4 are basic identical, and difference is, heat source generator is combustible gas combustion furnace, laser apparatus or graphite electric heater.The inside of the position of silicon material and the gas reaction Formed SiClx that contains carbon in combustible gas combustion furnace or graphite electric heater
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendments or supplement or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Claims (20)
1. the preparation method of a silicon carbide; it is characterized in that; in body of heater under vacuum environment or protection of inert gas, the silicon material of producing silicon carbide is melted or evaporated in the hot environment that exceedes 1300 DEG C and will melt or the silicon material of evaporation and gas or the liquid reactions Formed SiClx that contains carbon.
2. the preparation method of silicon carbide according to claim 1, is characterized in that, described silicon material is silicon.
3. according to the preparation method of the silicon carbide described in claim 2, it is characterized in that, described silicon material is purity higher than 99.99% silicon.
4. the preparation method of silicon carbide according to claim 1, is characterized in that, aerial in body of heater of the position of silicon material and the gas reaction Formed SiClx that contains carbon.
5. the preparation method of silicon carbide according to claim 1, is characterized in that, silicon material is joined in body of heater its melting or evaporation are gasified, and be ejected in the gas that contains carbon, reaction Formed SiClx.
6. the preparation method of silicon carbide according to claim 1, is characterized in that, by the gas that contains carbon or spouting of liquid to melt or the silicon material of evaporation gasification in, reaction Formed SiClx.
7. the preparation method of silicon carbide according to claim 1, is characterized in that, joining the gas reaction Formed SiClx that makes silicon material and contain carbon in above-mentioned body of heater after silicon material and the gas that contains carbon or liquid mixing.
8. according to the preparation method of the silicon carbide described in claim 1 or 4 or 5 or 6 or 7, it is characterized in that, described silicon material is siliceous compound.
9. according to the preparation method of the silicon carbide described in claim 1-7 any one, it is characterized in that, the heat source generator that melts or evaporate the hot environment of the described silicon material of gasification is plasma generator (1), combustible gas combustion furnace or laser apparatus or graphite electric heater.
10. according to the preparation method of the silicon carbide described in claim 9 any one, it is characterized in that the inside of the position of silicon material and the gas reaction Formed SiClx that contains carbon in plasma generator (1), combustible gas combustion furnace or graphite electric heater.
11. according to the preparation method of the silicon carbide described in claim 1-7 any one, it is characterized in that, described carbon elements gas is hydrocarbon, hydrocarbon polymer, fluorocarbon, carbon chlorine compound or contains one or several mixing in the gaseous compound of hydrocarbon fluorine element.
The preparation method of 12. silicon carbide according to claim 9, is characterized in that, centered by the thermal source providing, in concentrically ringed mode, above-mentioned carbon elements gas is provided in the preparation facilities of silicon carbide by described heat source generator.
The preparation method of 13. silicon carbide according to claim 12, is characterized in that, it is the identical or different several gases of composition that described carbon elements gas is provided in the preparation facilities of silicon carbide.
The preparation method of 14. silicon carbide according to claim 13, is characterized in that, the flow velocity of described gas is according to different from the distance of thermal source central point and adjust.
15. according to the preparation method of the silicon carbide described in claim 1-7 any one, it is characterized in that, the silicon carbide that to be mixed with containing weight percent in described silicon material be 0.1～10%.
The preparation facilities of 16. 1 kinds of silicon carbide, comprise body of heater (31) and be positioned at the crucible (4) of body of heater (31), be provided with elevating bracket (5) in the bottom of body of heater (31), above-mentioned crucible (4) is placed on elevating bracket (5), it is characterized in that, described body of heater (31) top is provided with the plasma generator (1) that jet orifice faces crucible (4), the inside of described plasma generator (1) has the inner chamber (18) of connection plasma generator (1) outlet, in inner chamber (18), be provided with airway (19), some toroidal membranes (14) taking airway (19) as axis are set on plasma generator (1) thus at plasma generator (1) if go out the individual concentric(al) circles outlet of interruption-forming (15), on plasma generator (1), be also provided with the import being connected with each outlet, be provided with venting port (6) in the bottom of body of heater (31).
The preparation facilities of 17. silicon carbide according to claim 16, is characterized in that, the import being connected with described inner chamber (18) is silicon material import (16).
18. according to the preparation facilities of the silicon carbide described in claim 16 or 17, it is characterized in that, described dividing plate (14) is two, is set in successively the outside of inner chamber (18) wall, forms respectively carbon elements gas feed (12) and secondary inlet (13).
19. according to the preparation facilities of the silicon carbide described in claim 16 or 17, it is characterized in that, is also provided with the silicon carbide generating is sucked to the suction opening (41) in crucible (4) on described crucible (4) outer side wall.
20. according to the preparation facilities of the silicon carbide described in claim 16 or 17, it is characterized in that, described body of heater (31) top is provided with shielding gas import (2).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410081038.6A CN103833035B (en) | 2014-03-06 | 2014-03-06 | Preparation method of silicon carbide |
| US15/123,657 US10407307B2 (en) | 2014-03-06 | 2015-02-12 | Production process for silicon carbide |
| PCT/CN2015/072942 WO2015131755A1 (en) | 2014-03-06 | 2015-02-12 | Method for preparing silicon carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410081038.6A CN103833035B (en) | 2014-03-06 | 2014-03-06 | Preparation method of silicon carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103833035A true CN103833035A (en) | 2014-06-04 |
| CN103833035B CN103833035B (en) | 2017-01-11 |
Family
ID=50796983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410081038.6A Expired - Fee Related CN103833035B (en) | 2014-03-06 | 2014-03-06 | Preparation method of silicon carbide |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US10407307B2 (en) |
| CN (1) | CN103833035B (en) |
| WO (1) | WO2015131755A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015131755A1 (en) * | 2014-03-06 | 2015-09-11 | 台州市一能科技有限公司 | Method for preparing silicon carbide |
| CN107512718A (en) * | 2017-08-07 | 2017-12-26 | 湖北工业大学 | A kind of preparation method and application of the nm-class silicon carbide material of high metal content |
| CN108069422A (en) * | 2017-12-25 | 2018-05-25 | 凯盛石墨碳材料有限公司 | A kind of method of graphite purification |
| CN108128777A (en) * | 2017-12-27 | 2018-06-08 | 江苏乐园新材料集团有限公司 | A kind of dynamic suspension is frictionally carbonized silicon preparation method and its heating unit |
| CN108463580A (en) * | 2015-09-24 | 2018-08-28 | 帕里杜斯有限公司 | Vapor phase growing apparatus and the technology for using silicon carbide derived from high-purity polymer |
| CN111663184A (en) * | 2020-06-23 | 2020-09-15 | 柯良节 | Novel plasma sublimation crystallization furnace and preparation method of silicon carbide crystal rod |
| CN112978732A (en) * | 2021-02-02 | 2021-06-18 | 北京绿清科技有限公司 | Production method and special production system of silicon carbide |
| CN112978731A (en) * | 2021-05-20 | 2021-06-18 | 浙江大学杭州国际科创中心 | Reaction device and preparation method of high-purity silicon carbide particles |
| CN114768714A (en) * | 2022-04-01 | 2022-07-22 | 安徽华东光电技术研究所有限公司 | Non-thermal arc plasma liquid fuel gasification device and method for improving gasification efficiency |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101617167B1 (en) * | 2015-08-12 | 2016-05-03 | 한국수력원자력 주식회사 | Plasma melter having side discharge gates |
| CN112960672B (en) * | 2021-02-10 | 2022-08-05 | 北京交通大学 | SiC particles with visible light response and preparation method thereof |
| CN113697812B (en) * | 2021-09-30 | 2023-01-13 | 中国航发北京航空材料研究院 | Preparation method of silicon carbide nanotube based on high-frequency electromagnetic field excitation |
| CN115010134B (en) * | 2022-06-21 | 2023-08-04 | 浙江六方碳素科技有限公司 | Device for preparing silicon carbide sponge by chemical vapor deposition |
| CN115557502A (en) * | 2022-09-14 | 2023-01-03 | 宁波日晟新材料有限公司 | Preparation method of single-layer two-dimensional silicon carbide crystal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5010270B1 (en) * | 1969-05-13 | 1975-04-19 | ||
| US4428755A (en) * | 1980-07-09 | 1984-01-31 | General Electric Company | Process for the production of silicone carbide composite |
| JPS6197126A (en) * | 1984-10-18 | 1986-05-15 | Mitsubishi Heavy Ind Ltd | Manufacture of fine particle of silicon carbide |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5010270Y1 (en) * | 1969-02-20 | 1975-04-01 | ||
| US4080508A (en) * | 1976-03-17 | 1978-03-21 | Greenewald Jr Herbert | Manufacture of carbides and the like |
| JPS6077114A (en) * | 1983-10-05 | 1985-05-01 | Nippon Steel Corp | Production of spherical sic powder |
| US5985024A (en) * | 1997-12-11 | 1999-11-16 | Northrop Grumman Corporation | Method and apparatus for growing high purity single crystal silicon carbide |
| US7776303B2 (en) * | 2006-08-30 | 2010-08-17 | Ppg Industries Ohio, Inc. | Production of ultrafine metal carbide particles utilizing polymeric feed materials |
| WO2009051888A1 (en) * | 2007-10-17 | 2009-04-23 | Ppg Industries Ohio, Inc. | Doped ultrafine metal carbide particles |
| US20100055017A1 (en) | 2008-09-03 | 2010-03-04 | Ppg Industries Ohio, Inc. | Methods for the production of ultrafine metal carbide particles and hydrogen |
| JP2013129558A (en) * | 2011-12-21 | 2013-07-04 | Bridgestone Corp | Method and apparatus for producing silicon fine particle |
| FR3013991B1 (en) * | 2013-11-29 | 2019-04-26 | Nanomakers | SUBMICRONIC PARTICLES COMPRISING ALUMINUM |
| CN103833035B (en) * | 2014-03-06 | 2017-01-11 | 台州市一能科技有限公司 | Preparation method of silicon carbide |
| JP6590203B2 (en) * | 2015-11-12 | 2019-10-16 | パナソニックＩｐマネジメント株式会社 | Fine particle production apparatus and fine particle production method |
-
2014
- 2014-03-06 CN CN201410081038.6A patent/CN103833035B/en not_active Expired - Fee Related
-
2015
- 2015-02-12 WO PCT/CN2015/072942 patent/WO2015131755A1/en active Application Filing
- 2015-02-12 US US15/123,657 patent/US10407307B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5010270B1 (en) * | 1969-05-13 | 1975-04-19 | ||
| US4428755A (en) * | 1980-07-09 | 1984-01-31 | General Electric Company | Process for the production of silicone carbide composite |
| JPS6197126A (en) * | 1984-10-18 | 1986-05-15 | Mitsubishi Heavy Ind Ltd | Manufacture of fine particle of silicon carbide |
Non-Patent Citations (2)
| Title |
|---|
| N.RAO ET AL.: "Synthesis of nanophase silicon, carbon, and silicon carbide powders using a plasma expansion process", 《J.MATER.RES.》, vol. 10, no. 8, 31 August 1995 (1995-08-31), XP055111043, DOI: 10.1557/JMR.1995.2073 * |
| 叶鑫南等: "一步法合成高纯度碳化硅粉体的研究", 《无机材料学报》, vol. 23, no. 2, 31 March 2008 (2008-03-31) * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015131755A1 (en) * | 2014-03-06 | 2015-09-11 | 台州市一能科技有限公司 | Method for preparing silicon carbide |
| TWI770769B (en) * | 2015-09-24 | 2022-07-11 | 美商佩利達斯股份有限公司 | Vapor deposition apparatus and techniques using high purity polymer derived silicon carbide |
| TWI719164B (en) * | 2015-09-24 | 2021-02-21 | 美商佩利達斯股份有限公司 | Vapor deposition apparatus and techniques using high purity polymer derived silicon carbide |
| TWI820738B (en) * | 2015-09-24 | 2023-11-01 | 美商佩利達斯股份有限公司 | Vapor deposition apparatus and techniques using high purity polymer derived silicon carbide |
| CN108463580A (en) * | 2015-09-24 | 2018-08-28 | 帕里杜斯有限公司 | Vapor phase growing apparatus and the technology for using silicon carbide derived from high-purity polymer |
| CN108463580B (en) * | 2015-09-24 | 2021-11-12 | 帕里杜斯有限公司 | Vapor deposition apparatus and techniques using high purity polymer-derived silicon carbide |
| CN107512718B (en) * | 2017-08-07 | 2019-10-11 | 湖北工业大学 | A kind of preparation method and application of the nm-class silicon carbide material of high metal content |
| CN107512718A (en) * | 2017-08-07 | 2017-12-26 | 湖北工业大学 | A kind of preparation method and application of the nm-class silicon carbide material of high metal content |
| CN108069422A (en) * | 2017-12-25 | 2018-05-25 | 凯盛石墨碳材料有限公司 | A kind of method of graphite purification |
| CN108128777B (en) * | 2017-12-27 | 2021-07-30 | 江苏乐园新材料集团有限公司 | Dynamic suspension friction type silicon carbide preparation method and heating device thereof |
| CN108128777A (en) * | 2017-12-27 | 2018-06-08 | 江苏乐园新材料集团有限公司 | A kind of dynamic suspension is frictionally carbonized silicon preparation method and its heating unit |
| CN111663184A (en) * | 2020-06-23 | 2020-09-15 | 柯良节 | Novel plasma sublimation crystallization furnace and preparation method of silicon carbide crystal rod |
| CN112978732A (en) * | 2021-02-02 | 2021-06-18 | 北京绿清科技有限公司 | Production method and special production system of silicon carbide |
| CN112978732B (en) * | 2021-02-02 | 2023-08-18 | 北京绿清科技有限公司 | Production method and special production system of silicon carbide |
| CN112978731A (en) * | 2021-05-20 | 2021-06-18 | 浙江大学杭州国际科创中心 | Reaction device and preparation method of high-purity silicon carbide particles |
| CN114768714A (en) * | 2022-04-01 | 2022-07-22 | 安徽华东光电技术研究所有限公司 | Non-thermal arc plasma liquid fuel gasification device and method for improving gasification efficiency |
Also Published As
| Publication number | Publication date |
|---|---|
| US20170081198A1 (en) | 2017-03-23 |
| US10407307B2 (en) | 2019-09-10 |
| CN103833035B (en) | 2017-01-11 |
| WO2015131755A1 (en) | 2015-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103833035A (en) | Preparation method of silicon carbide | |
| CN101570331B (en) | Preparation method of high-purity ultrafine spherical quartz powder | |
| US10040712B2 (en) | Process and apparatus for making a mineral melt | |
| CN100369811C (en) | Comprehensive utilization method of by-product for poycrystalline silicon production process | |
| CN1047663A (en) | The heat treating method of glass batch and equipment | |
| KR100214916B1 (en) | Process and device for the preparation of carbonblack from waste tires | |
| JP4889141B2 (en) | Method for producing fused silica particles | |
| CN2908510Y (en) | Multi-nozzle water coal fluid or pulverized coal gasification furnace for water coal fluid or pulverized coal gasification | |
| CN102260537A (en) | Device for preparing combustible gas by virtue of plasma pyrolysis and oxygen-enriched combustion-supporting material | |
| CN100445244C (en) | Method and structure of preventing channel of reactor for preparing ethyne by cracking plasma coal from coking | |
| WO2007102745A1 (en) | Method for the manufacture of pure silicon metal and amorphous silica by reduction of quartz (sio2) | |
| CN107099171A (en) | A kind of graphene strengthens carbon black preparation method | |
| CN102358849B (en) | Heat recovering type fuel gas preparation system and fuel gas preparation method thereof | |
| CN102086036B (en) | Process and equipment for continuously preparing nano carbon ball | |
| CN1210381C (en) | Method and device for using plasma to proceed coal gasification | |
| CN2460865Y (en) | Multi-nozzle opposed water-coal or coal dust gasification furnace with nozzle on top | |
| CN210885896U (en) | Plasma reactor for preparing carbon material by countercurrent cracking of gaseous hydrocarbon | |
| CN100551818C (en) | The method of preparing hydrogen by decomposing hydrogen sulfide | |
| JP5230051B2 (en) | Fine fused silica particles | |
| WO2023167268A1 (en) | Method for producing silicon monoxide | |
| CN1673075A (en) | Process of preparing diamond film with coal | |
| CN108713003A (en) | The manufacturing method of glass ingot | |
| CN107055534A (en) | The method that high-purity titanium carbide is prepared using low-purity titanium material | |
| JP5552157B2 (en) | Coal gasifier | |
| CA3219176A1 (en) | Plasma arc process and apparatus for the production of fumed silica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200109 Address after: West of 4th floor, building 3, No. 818, east section of development avenue, Taizhou City, Zhejiang Province Patentee after: Taizhou Yineng Science & Technology Co., Ltd. Address before: 318000, Zhejiang, Taizhou Province, 818 Eastern Road Development Avenue, 3, west side of the 4 Co-patentee before: Hoshino Masahiro Patentee before: Taizhou Yineng Science & Technology Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170111 Termination date: 20210306 |